Phenylcyclopentylamine fungicides



Un ted 31m? This invention; relates .to: new ,chemicalcompositions of matter. More specifically, it relates to new chemical compositions of the general formula v v V wherein )2 is an atom selected from-the group. consisting of hydrogen, halogen and their mixtures. Thus, when all the X are hydrogen, the-compound is 3-phenylcyclopentylamine. A wide variety ofrelated compounds contain combinations of halogen atoms and hydrogen atoms in the X positions. Thcse-compoundsjhave been found to be unusually active as pest control agents and particularlyas fungicides.

Thecompo'unds of this invention are prepared readily and in good-yield by the condensation of 3-aminocyclopentene with the appropriate phenyl compound in thepresence of acondensing agent such as anhydrous aluniinum chloride. .Ex'cess condensing agent isrequired,-

since thebasic-amino group. removes a mole of the acidicagent from?activeparticipationin the reaction, The reaction is generally carried out-by; adding-theamine to a stirred mixture of the condensing agent and-the phenyl compound, in an inert solvent ifdesired,-at ajtemperature' between about and 10 C. The mixture is then h'eated at or-slightlybelow reflux temperature for several hours-to completenthe reaction. The cooled reaction mixture is poured onto crushed ice and extracted with ether. The aqueous phase is :then made'basic with strong caustic and is extracted with ether. Thecombinedether' extracts are then dried, filtered, and distilled to give the desired 'product. v

' Suitable phenyl c'ompoundst-foruse 'inpr'oducin'g the new chemical compounds of thisinvention are, for example, benzene, v monochlorobeniene, ortho-Tdichlorobem zene, meta-dichloicibenzene,para-dichlorobenzene, 1,2,3- trichlorobenzene, 1,2,4-trichlorobenzen'e, l,3,5-'trichlorobenzene; 1,2,3,4-tetrachlorobenzene, l,2,3,5-tetrachlorobenaene, l,2,4,5-tetrachlorobeniene, pentachlorobenzene, and sirnilar halogenated compounds. The. resulting product of this invention when'ithe phenyl compound is, benzene is 3-phenylcyclopentylain'ine; When mon'ochlorobenzene is used, the product is a 3-(chlorophenyl)cyclopentylamine. When the-"di-, t'ri-, tetra-, or pentachlorobenzenes are used, the products are 3-(dichlorophenyl)- cyclopentylamine, 3-'(trichloroph enyl)cyclopentylamine, 3 (tetrachlorophenyl)cyelopentylamine, and 3 (pentachlorophenyl)cyclopentylamirie, respectively. Other halogen-substituted phenyl compoundsan be used in order to make X a halogen other than chlorine in the final product, Thus, monoiodobenzene, monobromobenzene, monofluofobenzene, or pfentabr'ofnobenzene;can be used as starting materials t o g'ive'3 (io'dophenyl)cyclopentyl 2,967,12 Patented Jan. 3, 196

annii gsf itir binoe "yl)'cy clopentylaniine, S-(flubi'bp yl) 9yc19pefi y a' l pentylaminel. respectively.

1 ,3 -chlorobromobenzene, which produces 3 eh1oro'-' bromophenyl)cyclopentylamine as the final product. i

Theco'mp ounds of'this invention have unusual activityas pesticides and particularly as fungicides. The co' p df 3-p'henyieyue enty amme,' for example, has ne fdpfid' to bfltolii'c "3 W d v ety of economically' I v 'P p fi r l p m nf carried out by th"e sli germination technique adopted' by the Committee on Standardization of l-iingicidal Tests of the American Phytopathblogical Society, measured concentrations of spores-of -Filsdrium'roseizm'were placed on glass'slides in contact with difierent';concentrationsof the compound being tested. Percentage germination of spores wastheti techniquein, which the test organism was Ste'h'zphy lzufn safcifiizfo'rhae} 3-phenylcyclopentylarnine showedanalog, value parts per million of 32. v

, Experiments wer also carried out for control of bean w en bean oliage; Pinto bean seedlings, grown under gFeenhouse conditions, were mounted on a special coin} poundturntable and'sprayed with the'various compounds" under test at several concentrations for 30 seconds ar- 30' pounds pressure. The plants were allowed to dry",- inoculated, with spore suspensions of the bean rust or ganisin,.Urbmycs'plmseoli, and place'd in an incubation chamber for 24' to' 48 hours. The plants werethen re moved and maintained under greenhouse conditions-fob 10 to 14 days, whereupon the number of rust pustules on the leaves of each plant were determined. When compared to untreated controls, the use of 3-phenylcyclo pen'tylamine at a concentration of 100 p.p.m. gave control of bean rust under these experimental conditions. When the compounds of this invention are used as pesticides, they are utilized in the manner recognizedin'the art. Thus the'ymay be dissolved in organic 'so'lve'n'ts suchasxylene or kerosene and used directly as sprayson the areaswhich are to be freed of the nude sirableorg'anisins. Similarly, they canbe'used as sus pensions or emulsions in water by formulation with organic solvents and surface-active agents. They canalso be formulated in other inert diluents such as the ta'cs or clays and thus" be applied by dusting or by 77 liter, 3-necked, round-bottomed flask fitted with a watercooled reflux condenser (calcium chloride drying tube), thermometer, dropping funnel, and mechanical stirrer. The fl'ask"was co'o'led with ice" to maintain a temperature of 0-5 C-. inthereaction'mixture:while 3-"aminocyclopentene (49.9 g.; 0.6 mole) in 54 ml. benzene was added dropwise A t6ta'l of'432 ml. 4.8 moles) of benzene and 3-(pl'ltabrfimdphifi ncye Products with mixtures of halogen, in addition to liydi'bgilgatbm's in" positions can also-be made, for example, by the use"of"' was thus employed. When the addition of the amine was complete, the reaction mixture was heated to reflux temperature (about 82 C.) and was stirred and refluxed for 8 hours. The cooled reaction mixture was poured slowly onto 400 ml. cracked ice, and the mixture was stirred for 20 minutes. The mixture separated into layers in a separatory funnel, and the uppermost benzene layer was discarded. The lower, clear aqueous layer was found to contain no product, and hence the dark center layer was made basic with sodium hydroxide and extracted three times with 200-m1. portions of ether. The combined ether extracts were dried over anhydrous potassium carbonate, filtered, and distilled. After removal of the ether, distillation of the residue in vacuo gave 80.4 g. (83% of theory) of S-phenylcyclopentylamine having a boiling range of 119 to 121 mm. pressure and an index of refraction (D line) of 1.5464 at 22 C. An analytical sample of the product distilled at 129 to 130 C. at 16 mm. pressure.

Analysis for C H N.-Calculated: C, 81.93%; H, 9.38%; N, 8.69%. Found: C, 81.83%; H, 9.53%; N, 8.77%.

EXAMPLE 2 Preparation of 3-(4'-chlorophenyl)cyclopentylamine Monochlorobenzene (448 g.; 4.0 moles) and anhydrous aluminum chloride (133 g.; 1 mole) are mixed in a 1-liter, 3-necked, round-bottomed flask fitted as described in Example 1. The reaction mixture is cooled by immersing the flask in ice, and 3-aminocyclopentene (41 g.; 0.5 mole) is added dropwise while the reaction mixture is stirred vigorously and maintained at a temperature of -10" C. After all the amine has been added, the reaction mixture is heated to reflux and is refluxed and stirred for hours to complete the reaction. The reaction mixture is then cooled and poured onto crushed ice and extracted with ether. Work-up of the extract as described in Example 1 and fractionation of the residue in vacuo gives the desired 3-(4'-chlorophenyl)cyclopentylamine.

EXAMPLE 3 Preparation of 3-(pentachlorophenyl)cyclopentylamine A reaction is carried out in the apparatus (2-liter flask) and in the manner described in Example 1 with anhydrous aluminum chloride (133 g.; 1 mole), 3-aminocyclopentene (41 g.; 0.5 mole) and pentachlorobenzene (1000 g.; 4.0 moles) in 1000 cc. of carbon disulfide. Work-up of the reaction product as described in Example 1 gives the desired compound, 3-pentachlorophenyl)- cyclopentylamine.

EXAMPLE 4 Preparation of 3-(3',4'-dibrom0phenyl)cyclopentylamine A reaction is carried out in the apparatus and in the manner described in Example 1 with anhydrous aluminum chloride (133 g.; 1 mole), 3-aminocyclopentene (41 g.; 0.5 mole) and o-dibromobenzene (944 g.; 4.0 moles). The product is worked up in the manner described in Example 1 to give the desired compound, 3-(3',4'-dibromophenyl) cyclopentylamine.

EXAMPLE 5 Preparation of an emulsifiable concentrate of 3-(34'-dibromophenyl) cyclopentylamine The following concentrate is prepared by mixing the C. at 12' '4 ingredients intimately in the given percentage proportions by weight:

Percent 3(3,4-dibromophenyl)cyclopentylamine Antarox A-400 40 Methanol 35 Antarox A-400 is the trade name under which a nonionic detergent of the aromatic polyethylene glycol ether type is sold. The above concentrate is diluted with water to the desired concentration for use.

EXAMPLE 6 Preparation of an emalsifiable concentrate of 3-phenylcyclopentylamine The following ingredients are mixed thoroughly in the given percentage proportions by weight:

Percent 3-phenylcyclopentylamine 59 Xylene 10 Triton X-l00 5 Kerosene 26 Triton X-IOO is the trade name under which an emulsifier of the alkyl aryl polyether alcohol type is sold. The above concentrate is diluted with water to the desired concentration for use.

EXAMPLE 7 Preparation of a dust from 3-(pentachlorophenyl)cyclopentylamine 3-(pentachlorophenyl)cyclopentylamine (65% by weight) is heated in a melt kettle with xylene (35% by weight) until solution is efiected. Attapulgite clay carrier is placed in a ribbon blender, and sufficient 3-pentachlorophenyl)cyclopentylamine solution is sprayed in to give a 5% concentration of the chemical on the carrier. After pre-blending for 5 to 10 minutes, the formulation is ground to the desired particle size and transferred to a ribbon after-blender, where it is blended for 10 to 15 minutes before use.

While the outstanding utility of the compounds of this invention is in the field of control of undesirable fungal growth, the compounds are useful for a variety of other purposes. Aside from their applicability as new chemical intermediates, they have activity against other types of undesirable growth, such as bacteria. The compounds in which at least one of the X atoms is bromine, for example, are effective bacteriostats or bactericides. While the free amine compounds of this invention have been specifically described above, it is understood'that for any and all the uses described, the compounds can also be used in the form of their acid salts, such as the hydrochlorides, sulfates, phosphates, and the like.

i What is claimed in this invention is:

- 1. A method of destroying undesirable fungi which comprises contacting said fungi with a fungicidal composition comprising an inert carrier and as an essential active ingredient, in a quantity which is injurious to said fungi, a compound of the formula wherein each X is an atom selected from the group consisting of hydrogen, chlorine and bromine.

2. A fungicidal composition comprising an inert carwherein each X is an atom selected from the group conrier and a fungicidal toxic amount of a compound of the sisting of hydrogen, chlorine and bromine.

formula References Cited in the file of this patent 1 X 5 UNITED STATES PATENTS 1 21 312' -x 2,248,925 Lincoln ct al July 15, 1941 2,520,516 Van Zoeren Aug. 29, 1950 X X OTHER REFERENCES 10 Burton et a1.: Journal of the Chemical Society (1939), 

1. A METHOD OF DESTROYING UNDESIRABLE FUNGI WHICH COMPRISES CONTACTING SAID FUNGI WITH A FUNGICIDAL COMPOSITION COMPRISING AN INERT CARRIER AND AS AN ESSENTIAL ACTIVE INGREDIENT, IN A QUANTITY WHICH IS INJURIOUS TO SAID FUNGI, A COMPOUND OF TO FORMULA 